CA1304415C - Process for the preparation of fluoroalkyl perfluorovinyl ethers - Google Patents
Process for the preparation of fluoroalkyl perfluorovinyl ethersInfo
- Publication number
- CA1304415C CA1304415C CA000547270A CA547270A CA1304415C CA 1304415 C CA1304415 C CA 1304415C CA 000547270 A CA000547270 A CA 000547270A CA 547270 A CA547270 A CA 547270A CA 1304415 C CA1304415 C CA 1304415C
- Authority
- CA
- Canada
- Prior art keywords
- range
- process according
- preparation
- fluoroalkoxy
- dimethylformamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/17—Unsaturated ethers containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
Abstract
(Case T 3558) PROCESS FOR THE PREPARATION OF
FLUOROALKYL PERFLUOROVINYL ETHERS
Abstract of the Disclosure A process for the preparation of fluoroalkyl ethers of the formula:
(I) wherein:
Y is Br or F;
X is F, Cl or Br or their mixtures when n is equal to or higher than 2;
n is within the range of from 0 to 4;
Rf represents a perfluoroalkylene radical containing from 1 to 8 carbon atoms.
The process is characterized in that a fluoroalkoxy perfluoroacyl fluoride of the formula:
(II)
FLUOROALKYL PERFLUOROVINYL ETHERS
Abstract of the Disclosure A process for the preparation of fluoroalkyl ethers of the formula:
(I) wherein:
Y is Br or F;
X is F, Cl or Br or their mixtures when n is equal to or higher than 2;
n is within the range of from 0 to 4;
Rf represents a perfluoroalkylene radical containing from 1 to 8 carbon atoms.
The process is characterized in that a fluoroalkoxy perfluoroacyl fluoride of the formula:
(II)
Description
~0~4~L~
Description of the Invention The present invention relates to the preparation of fluoroalkyl perfluorovinyl ethers. More precisely, it relates to a process for the preparation of fluoroalkyl perfluorovinyl ethers having the formula:
Y_Rf-o-(cF-cF2-o)n-cF=cF2 wherein:
Y is Br or F;
X is Fj Cl or Br or their mixtures when n is equal to or higher than 2;
n is within the range of from O to 4;
Rf represents a perfluoroalkylene radical containing from 1 to 8 C atoms.
The fluoroalkyl perfluorovinyl ethers are useful as monomers for copolymerization with fluorinated olefins, and in particular tetrafluoroethylene, vinylidene fluoride and hexafluoropropene.
The introduction of these vinyl ethers in the so-obtained plastic polymers leads to better properties of processability of the polymers, and a higher flexibility of the manufactured articles.
Furthermore, when Y is Br, a potentially reactive site is inserted into the polymer which may be used for additional réactions which otherwise would not be possible in perfluorinated materials. The thus-obtained polymers may be used, e.g., in chlorinè-alkali cells, as ion-exchange membranes.
: ; :: :
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~3~ 15 The preparation of the fluoroalkyl perfluorovinyl ethers is known starting from the corresponding acyl fluorides by decarboxylation of the acyl fluoride by heating up to 300C in the presence of activators, such as ZnO hnd SiO2, and possibly in the presence of salifying agents. But such ~ synthesis route involves the formation of considerable amounts of secondary and tertiary isomers of the vinyl ether, as described in U.S. Patent No. 3,896,179, i.e., compounds of the types:
-CF-O-C~=CF2 (second~ry isomer) -b-O-CF-CF2 (tertiary isomer) The presence of these isomers in the vinyl ether is highly undesirable, because they can act as chain-transfer agents in the subsequent copolymerization, giving rise to copolymers with a too low molecular weight.
Alsô processes are known which involve a salification of the acyl fluoride with salifying agents of the sodium carbonate type, in solvents of the glyme type, and a subsequent decarboxylation, e.g., at 100 - 150C. These processes can be schematically shown as follows:
R-O-CF-COF
; ~ C~3 wherein R is a fluoroalkyl radical _2_ >3 R-O-CF-COONa decarboxylation R-O-CF=CF2 + NaF + CO2.
One of these processes is disclosed in U.S. Patent No. 3,291,843.
:~ ~ .
;l ~ Li5 When the vinyl ether is obtained by means of one of ¦ these processes, it may contain considerable amounts of hydrogenated byproduct, of the ¦ -CF2-0-CFH-CF3 type.
¦ The presence of hydrogenated products at a concentration higher than certain levels involves the presence of particularly reactive sites (-CH bonds), which are undesirable in the copolymerization process. It has furthermore been verified that copolymers obtained from vinyl ethers polluted by hydrogenated byproducts show insurmountable problems in the extrusion process, and lead to the obtention of manufactured articles having clearly unsatisfactory applicative properties.
An object of the present invention is therefore to provide a process for the preparation of 1uoroalkyl ¦ perfluorovinyl ethers of formula (I) by starting from the ¦ corresponding acyl fluorides, wherein the obtained product is ¦ free from secondary and tertiary isomers, and is substantially ¦ free from hydrogenated byproduct.
¦ Another object is to provide a process which gives very ¦ high yields of fluoroalkyl perfluorovinyl ethers.
These and still further objects are achieved by the ~process of the present invention for the preparation of fluoroalkyl perfluorovinyl ethers of formula (I).
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The prooess is ~har~cterized in th~t ~ flL~oro~lkoxy perfluoroacyl fluoride of formula:
Y-Rf-O-(fF-CF2-O)n-CF-COF (II) is slowly heated with a salifying agent and a solvent, in the presence of a catalytic amount of N,N-dimethylformamide, reaching an end temperature within the range of from 60 to 150C.
In acaordance with the present invention, it has been discovered that by operating in the presence of catalytic amounts of N,N-dimethylformamide and slowly heating up to a temperature within the range of from 60 to 150C, the thus-obtained product is free from secondary and tertiary isomers, and is substantially free from hydrogenated byproduct; and furthermore very high yields are obtained.
By the expression "substantially free" from hydrogenated byproduct, it is meant that such byproduct is present in a maximum amount not higher than 5~ by weight in the reaction products. Often, it is present in an amount not higher than about 0.5% by weight.
The amount of N,N-dimethylformamide is generally within the range of from 0.1 to 20% by weight relative to the acyl fluoride (II), and preferably in the range of from 0.5 to 5%.
Especially suitable organic solvents are those of the glyme type.
Especially suitable salifying agents for the acyl fluoride (II) are the alkali metal carbonates and alkaline-earth metal carbonates.
~~5~ .
, ' : : :
::
1304~L15 The amount of salifying agent is not critical. It may range from the stoichiometric amount to an excess, e.g., about 50%, relative to the stoichiometric amount.
For the purpose of obtaining a vinyl ether having a high purity level, it is necessary to thoroughly dry the solvent and the salifying agent.
Starting from an acyl fluoride (II) wherein the value of ~n is zero is preferred. Also starting from an acyl fluoride wherein the radical Rf contains from 2 to 3 C atoms is prefèrred.
The heating of the reaction mixture takes place slowly, until the end temperature within the range of from 60 to 150C, and preferably in the range of from 110 to 140C, is reached.
Usually, the heating of the reaction medium, to maintain it at the end temperature, is continued over a certain time, e.g. over 2 to 8 hours.
The duration of the slow heating step is, e.g., from 1 to 6 hours.
The following examples are supplied for the purpose of illustrating the invention without thereby limiting it.
Example 1 In the present example, to be compared to Example 2, N,N-dimethylformamide is not used.
To a 250-ml reactor equipped with stirrer, thermometer, and distillation column with condensor, 50 ml of anhydrous diglyme and 50 g of anhydrous K2C03 are charged.
At room temperature, 83 g (0.25 mol) of 2-perfluoropropoxy-perfluoropropionyl fluoride :
_~_ ~3~)44~i are slowly added in such a WQy that the temperature ~f the reaction mixture does not exceed 30C.
The reaction mass is then heated 1 hour at 35C, then 1 hour at 45C, and 1 hour at 60C; now it is possible to start the product refluxing through the distillation column.
For completing the reaction, the mixture is Icept heated at 120C for 6 hours.
Fifty-eight grams of a reaction product was obtained, which was identified by lH-N.M.R. and 19F-N.M.R. analyses, and mass-spectrophotometry.
80% of product is constituted by perfluoropropyl vinyl ether (46.4 g - 0.174 mol) and the residual 20% thereof is heptafluoropropyl 1,2,2,2-tetrafluoroethyl ether (C3F7-O-CFH-CF3) (11.6 g). Reaction conversion = 100%, selectivity to and yield of perfluoropropyl vinyl ether = 69.7%.
During the reaction, small arnounts of unidentified uncondensable products are formed.
Example 2 To a reaction equipment analogous to that described in the preceding Example 19 50 ml of anhydrous diglyme, 1 ml (0.994 g) of N,N-dimethylformamide, and 50 g of anIlydrous K2CO3 are charged.
At room temperature, 83 g (0.25 mol) of 2-perfluoropropoxy peifluoroproplonyl fluoride are slowly added in such a way that the temperature of the reaction mixture does not exceed 3QC.
~; ~ ~ ~_q_ .
~ :
~: ~
: ~
-ll 13~9~4~5 The reaction mass is then heated 1 hour at 35C, then 1 hour at 45C, and 1 hour at 60C; now, it is possible to start to draw the product refluxing through the distillation column.
For completing the reaction, the mixture is kept heated at 120C for 6 hours.
64.4 grams were obtained of a reaction mixture, which is constituted by:
64.07 g of perfluoropropyl vinyl ether;
0.32 g of heptafluoropropyl 1,2,2,2-tetrafluoroethyl ether.
Conversion: 100%, selectivity to and yield of perfluoropropyl vinyl ether: 96%.
. ~
In the present example, to be compared to Example 4, no N,N-dimethylformamide is used.
Five hundred ml of anhydrous diglyme and 400 g of anhydrous NaaCO3 are charged to a 2,000-ml four-neck flask equipped with stirrer, thermometer, dropping funnel and reflux condenser connected to a Claisen distillation apparatus.
860 g are added dropwise of acyl fluoride CF2Br-cF2-o-cF-coF
with the inner temperature being maintained at approximately 20C. During the addition time, gas evolves. After the end of the dripping, stirring is continued for 1 hour. The heating is ~then started, with the temperature being p~ogressively increased up~ to 130C: 1 hour at 80C, 1 hour at 100C, 1 hour at 120C.
The evolution of gas starts again at 130C. Now it is possible to start to draw off the product, which is collected inside a trap ed rt -l8C.
~;
~ .
~30~S
For completing the reaction, the reaction mixture is kept heated at 130C for 3 hours.
The collected product is purified by fractional distillation. 400 grams are obtained of a fraction boiling at 56-57C, which contains 89.3% by weight of CF2Br-CF2-0-CF=CF2 and 10.7% by weight of CF2Br-CF2-O-CFH-CF3.
The products were characterized by I.R. spectroscopy and 19F~N.M.R. and lH-N.M.R.
Example 4 The prepàration is carried out accordin~ to the procedures of Example 3, by using 500 g of anhydrous Na2CO3, 600 ml of anhydrous diglyme, 1,000 g of the same acyl fluoride of Example 3, and 10 g of N,N-dimethylformamide. 650 g are obtained of a product which is constituted by 96% by weight of CF2Br-CF2-0-CF=CF2 and 4% by weight of hydrogenated byproduct.
The products were characterized by I.R. spectroscopy and l9 .M.R. and lH-N.M.R.
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Description of the Invention The present invention relates to the preparation of fluoroalkyl perfluorovinyl ethers. More precisely, it relates to a process for the preparation of fluoroalkyl perfluorovinyl ethers having the formula:
Y_Rf-o-(cF-cF2-o)n-cF=cF2 wherein:
Y is Br or F;
X is Fj Cl or Br or their mixtures when n is equal to or higher than 2;
n is within the range of from O to 4;
Rf represents a perfluoroalkylene radical containing from 1 to 8 C atoms.
The fluoroalkyl perfluorovinyl ethers are useful as monomers for copolymerization with fluorinated olefins, and in particular tetrafluoroethylene, vinylidene fluoride and hexafluoropropene.
The introduction of these vinyl ethers in the so-obtained plastic polymers leads to better properties of processability of the polymers, and a higher flexibility of the manufactured articles.
Furthermore, when Y is Br, a potentially reactive site is inserted into the polymer which may be used for additional réactions which otherwise would not be possible in perfluorinated materials. The thus-obtained polymers may be used, e.g., in chlorinè-alkali cells, as ion-exchange membranes.
: ; :: :
i ~
:: : :
: ~ - - ~ . , ' .
~3~ 15 The preparation of the fluoroalkyl perfluorovinyl ethers is known starting from the corresponding acyl fluorides by decarboxylation of the acyl fluoride by heating up to 300C in the presence of activators, such as ZnO hnd SiO2, and possibly in the presence of salifying agents. But such ~ synthesis route involves the formation of considerable amounts of secondary and tertiary isomers of the vinyl ether, as described in U.S. Patent No. 3,896,179, i.e., compounds of the types:
-CF-O-C~=CF2 (second~ry isomer) -b-O-CF-CF2 (tertiary isomer) The presence of these isomers in the vinyl ether is highly undesirable, because they can act as chain-transfer agents in the subsequent copolymerization, giving rise to copolymers with a too low molecular weight.
Alsô processes are known which involve a salification of the acyl fluoride with salifying agents of the sodium carbonate type, in solvents of the glyme type, and a subsequent decarboxylation, e.g., at 100 - 150C. These processes can be schematically shown as follows:
R-O-CF-COF
; ~ C~3 wherein R is a fluoroalkyl radical _2_ >3 R-O-CF-COONa decarboxylation R-O-CF=CF2 + NaF + CO2.
One of these processes is disclosed in U.S. Patent No. 3,291,843.
:~ ~ .
;l ~ Li5 When the vinyl ether is obtained by means of one of ¦ these processes, it may contain considerable amounts of hydrogenated byproduct, of the ¦ -CF2-0-CFH-CF3 type.
¦ The presence of hydrogenated products at a concentration higher than certain levels involves the presence of particularly reactive sites (-CH bonds), which are undesirable in the copolymerization process. It has furthermore been verified that copolymers obtained from vinyl ethers polluted by hydrogenated byproducts show insurmountable problems in the extrusion process, and lead to the obtention of manufactured articles having clearly unsatisfactory applicative properties.
An object of the present invention is therefore to provide a process for the preparation of 1uoroalkyl ¦ perfluorovinyl ethers of formula (I) by starting from the ¦ corresponding acyl fluorides, wherein the obtained product is ¦ free from secondary and tertiary isomers, and is substantially ¦ free from hydrogenated byproduct.
¦ Another object is to provide a process which gives very ¦ high yields of fluoroalkyl perfluorovinyl ethers.
These and still further objects are achieved by the ~process of the present invention for the preparation of fluoroalkyl perfluorovinyl ethers of formula (I).
: :
~: ~ : .
` ~ _ 4 _ ~:
1~
- 13~
The prooess is ~har~cterized in th~t ~ flL~oro~lkoxy perfluoroacyl fluoride of formula:
Y-Rf-O-(fF-CF2-O)n-CF-COF (II) is slowly heated with a salifying agent and a solvent, in the presence of a catalytic amount of N,N-dimethylformamide, reaching an end temperature within the range of from 60 to 150C.
In acaordance with the present invention, it has been discovered that by operating in the presence of catalytic amounts of N,N-dimethylformamide and slowly heating up to a temperature within the range of from 60 to 150C, the thus-obtained product is free from secondary and tertiary isomers, and is substantially free from hydrogenated byproduct; and furthermore very high yields are obtained.
By the expression "substantially free" from hydrogenated byproduct, it is meant that such byproduct is present in a maximum amount not higher than 5~ by weight in the reaction products. Often, it is present in an amount not higher than about 0.5% by weight.
The amount of N,N-dimethylformamide is generally within the range of from 0.1 to 20% by weight relative to the acyl fluoride (II), and preferably in the range of from 0.5 to 5%.
Especially suitable organic solvents are those of the glyme type.
Especially suitable salifying agents for the acyl fluoride (II) are the alkali metal carbonates and alkaline-earth metal carbonates.
~~5~ .
, ' : : :
::
1304~L15 The amount of salifying agent is not critical. It may range from the stoichiometric amount to an excess, e.g., about 50%, relative to the stoichiometric amount.
For the purpose of obtaining a vinyl ether having a high purity level, it is necessary to thoroughly dry the solvent and the salifying agent.
Starting from an acyl fluoride (II) wherein the value of ~n is zero is preferred. Also starting from an acyl fluoride wherein the radical Rf contains from 2 to 3 C atoms is prefèrred.
The heating of the reaction mixture takes place slowly, until the end temperature within the range of from 60 to 150C, and preferably in the range of from 110 to 140C, is reached.
Usually, the heating of the reaction medium, to maintain it at the end temperature, is continued over a certain time, e.g. over 2 to 8 hours.
The duration of the slow heating step is, e.g., from 1 to 6 hours.
The following examples are supplied for the purpose of illustrating the invention without thereby limiting it.
Example 1 In the present example, to be compared to Example 2, N,N-dimethylformamide is not used.
To a 250-ml reactor equipped with stirrer, thermometer, and distillation column with condensor, 50 ml of anhydrous diglyme and 50 g of anhydrous K2C03 are charged.
At room temperature, 83 g (0.25 mol) of 2-perfluoropropoxy-perfluoropropionyl fluoride :
_~_ ~3~)44~i are slowly added in such a WQy that the temperature ~f the reaction mixture does not exceed 30C.
The reaction mass is then heated 1 hour at 35C, then 1 hour at 45C, and 1 hour at 60C; now it is possible to start the product refluxing through the distillation column.
For completing the reaction, the mixture is Icept heated at 120C for 6 hours.
Fifty-eight grams of a reaction product was obtained, which was identified by lH-N.M.R. and 19F-N.M.R. analyses, and mass-spectrophotometry.
80% of product is constituted by perfluoropropyl vinyl ether (46.4 g - 0.174 mol) and the residual 20% thereof is heptafluoropropyl 1,2,2,2-tetrafluoroethyl ether (C3F7-O-CFH-CF3) (11.6 g). Reaction conversion = 100%, selectivity to and yield of perfluoropropyl vinyl ether = 69.7%.
During the reaction, small arnounts of unidentified uncondensable products are formed.
Example 2 To a reaction equipment analogous to that described in the preceding Example 19 50 ml of anhydrous diglyme, 1 ml (0.994 g) of N,N-dimethylformamide, and 50 g of anIlydrous K2CO3 are charged.
At room temperature, 83 g (0.25 mol) of 2-perfluoropropoxy peifluoroproplonyl fluoride are slowly added in such a way that the temperature of the reaction mixture does not exceed 3QC.
~; ~ ~ ~_q_ .
~ :
~: ~
: ~
-ll 13~9~4~5 The reaction mass is then heated 1 hour at 35C, then 1 hour at 45C, and 1 hour at 60C; now, it is possible to start to draw the product refluxing through the distillation column.
For completing the reaction, the mixture is kept heated at 120C for 6 hours.
64.4 grams were obtained of a reaction mixture, which is constituted by:
64.07 g of perfluoropropyl vinyl ether;
0.32 g of heptafluoropropyl 1,2,2,2-tetrafluoroethyl ether.
Conversion: 100%, selectivity to and yield of perfluoropropyl vinyl ether: 96%.
. ~
In the present example, to be compared to Example 4, no N,N-dimethylformamide is used.
Five hundred ml of anhydrous diglyme and 400 g of anhydrous NaaCO3 are charged to a 2,000-ml four-neck flask equipped with stirrer, thermometer, dropping funnel and reflux condenser connected to a Claisen distillation apparatus.
860 g are added dropwise of acyl fluoride CF2Br-cF2-o-cF-coF
with the inner temperature being maintained at approximately 20C. During the addition time, gas evolves. After the end of the dripping, stirring is continued for 1 hour. The heating is ~then started, with the temperature being p~ogressively increased up~ to 130C: 1 hour at 80C, 1 hour at 100C, 1 hour at 120C.
The evolution of gas starts again at 130C. Now it is possible to start to draw off the product, which is collected inside a trap ed rt -l8C.
~;
~ .
~30~S
For completing the reaction, the reaction mixture is kept heated at 130C for 3 hours.
The collected product is purified by fractional distillation. 400 grams are obtained of a fraction boiling at 56-57C, which contains 89.3% by weight of CF2Br-CF2-0-CF=CF2 and 10.7% by weight of CF2Br-CF2-O-CFH-CF3.
The products were characterized by I.R. spectroscopy and 19F~N.M.R. and lH-N.M.R.
Example 4 The prepàration is carried out accordin~ to the procedures of Example 3, by using 500 g of anhydrous Na2CO3, 600 ml of anhydrous diglyme, 1,000 g of the same acyl fluoride of Example 3, and 10 g of N,N-dimethylformamide. 650 g are obtained of a product which is constituted by 96% by weight of CF2Br-CF2-0-CF=CF2 and 4% by weight of hydrogenated byproduct.
The products were characterized by I.R. spectroscopy and l9 .M.R. and lH-N.M.R.
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Claims (9)
1. Process for the preparation of a fluoroalkyl perfluorovinyl ether of the formula (I) wherein:
Y is Br or F;
X is F, Cl or Br or their mixtures when n is equal to or higher than 2;
n is within the range of from 0 to 4;
Rf represents a perfluoroalkylene radical containing from 1 to 8 C
atoms;
characterized in that a fluoroalkoxy perfluoroacyl fluoride of the formula:
(II) is slowly heated with a salifying agent and a solvent, in the presence of a catalytic amount of N,N-dimethylformamide, with an end temperature within the range of from 60° to 150°C.
Y is Br or F;
X is F, Cl or Br or their mixtures when n is equal to or higher than 2;
n is within the range of from 0 to 4;
Rf represents a perfluoroalkylene radical containing from 1 to 8 C
atoms;
characterized in that a fluoroalkoxy perfluoroacyl fluoride of the formula:
(II) is slowly heated with a salifying agent and a solvent, in the presence of a catalytic amount of N,N-dimethylformamide, with an end temperature within the range of from 60° to 150°C.
2. Process according to Claim 1, characterized in that the amount of N,N-dimethylformamide is within the range of from 0.1 to 20% by weight relative to the fluoroalkoxy perfluoroacyl fluoride (II)
3. Process according to Claim 1, characterized in that the amount of N,N-dimethylformamide is within the range of from 0.5 to 5% by weight relative to the fluoroalkoxy perfluoroacyl fluoride (II).
4. Process according to Claims 1, 2 or 3 characterized in that the solvent is selected from the group consisting of the glymes.
5. Process according to Claim 1, 2 or 3 characterized in that the salifying agent is selected from the group consisting of the carbonates of alkali and alkali-earth metals.
6. Process according to Claim 5 characterized in that the salifying agent is an alkali metal carbonate.
7. Process according to Claims 1, 2 or 3 characterized in that in the fluoroalkoxy perfluoroacyl fluoride (II), the value of n is zero.
8. Process according to Claims 1, 2 or 3 characterized in that in the fluoroalkoxy perfluoroacyl fluoride (II), the radical Rf contains from 2 to 3 C atoms.
9. Process according to Claim 1, 2 or 3, characterized in that an end temperature within the range of from 110° to 140°C
is reached.
is reached.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT21759/86A IT1197821B (en) | 1986-09-19 | 1986-09-19 | PROCEDURE FOR PREPARING DIFLUOROALKYL PERFLUOROVINIL ETERI |
| IT21759A/86 | 1986-09-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1304415C true CA1304415C (en) | 1992-06-30 |
Family
ID=11186463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000547270A Expired - Lifetime CA1304415C (en) | 1986-09-19 | 1987-09-18 | Process for the preparation of fluoroalkyl perfluorovinyl ethers |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4772756A (en) |
| EP (1) | EP0260773B1 (en) |
| JP (1) | JP2517313B2 (en) |
| CA (1) | CA1304415C (en) |
| DE (1) | DE3775867D1 (en) |
| ES (1) | ES2037704T3 (en) |
| IT (1) | IT1197821B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5349093A (en) * | 1987-04-25 | 1994-09-20 | Daikin Industries, Ltd. | Fluorovinyl ether |
| EP0290848B1 (en) * | 1987-04-25 | 1991-07-31 | Daikin Industries, Limited | Novel fluorovinyl ether |
| IT1226147B (en) * | 1988-07-04 | 1990-12-19 | Ausimont Spa | PROCESS FOR THE PREPARATION OF PERFLUORO (2 BROMOETHYLVINYLETE). |
| JP2610538B2 (en) * | 1990-04-13 | 1997-05-14 | 日本メクトロン株式会社 | Purification method of perfluoro (propyl vinyl ether) |
| US5268511A (en) * | 1992-03-27 | 1993-12-07 | E. I. Du Pont De Nemours And Company | Production of trifluorovinyl ethers |
| DE4219764A1 (en) * | 1992-06-17 | 1993-12-23 | Bayer Ag | Cyclopolymerizable fluorine compounds, process for their preparation and thermoplastic fluoropolymers obtainable therefrom |
| JP3360689B2 (en) * | 1992-06-26 | 2002-12-24 | ダイキン工業株式会社 | Method for producing fluorinated vinyl ether |
| US5350497A (en) * | 1993-05-21 | 1994-09-27 | E. I. Du Pont De Nemours And Company | Production of perfluoro(alkyl vinyl ethers) |
| US5777179A (en) * | 1996-05-24 | 1998-07-07 | E. I. Du Pont De Nemours And Company | Co-production of perfluoromethyl perfluorovinyl ether and perfluoroethyl perfluorovinyl ether |
| KR100631714B1 (en) * | 2004-06-30 | 2006-10-09 | 엘지전자 주식회사 | Apparatus and method for improved video signal rate control of a mobile terminal |
| US7176331B2 (en) | 2005-06-30 | 2007-02-13 | 3M Innovative Properties Company | Method of making fluorinated vinyl ethers |
| CN102516039A (en) | 2011-11-16 | 2012-06-27 | 中昊晨光化工研究院 | Preparation method of fluorine-containing vinyl ether |
| CN103864583A (en) * | 2012-12-13 | 2014-06-18 | 中化蓝天集团有限公司 | Heptafluoropropyl-1,2,2,2-tetrafluoroethyl ether preparation method |
| CN103965023B (en) * | 2013-01-31 | 2016-05-11 | 中化蓝天集团有限公司 | A kind of preparation method of fluoro-alkyl vinyl ethers |
| CN105017467A (en) * | 2015-07-31 | 2015-11-04 | 苏州新区特氟龙塑料制品厂 | Preparation method of PFA soluble polytetrafluoroethylene |
| CN108689811B (en) * | 2018-03-23 | 2021-05-18 | 金华永和氟化工有限公司 | Method and reaction system for preparing perfluoroalkyl vinyl ether |
| CN113150262B (en) * | 2021-04-22 | 2022-07-05 | 浙江巨化技术中心有限公司 | End capping method of perfluoropolyether |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3321532A (en) * | 1963-10-08 | 1967-05-23 | Du Pont | Fluorocarbon ethers |
| US3291843A (en) * | 1963-10-08 | 1966-12-13 | Du Pont | Fluorinated vinyl ethers and their preparation |
| US4515989A (en) * | 1980-06-11 | 1985-05-07 | The Dow Chemical Company | Preparation decarboxylation and polymerization of novel acid flourides and resulting monomers |
| JPS5885831A (en) * | 1981-11-18 | 1983-05-23 | Asahi Glass Co Ltd | Prefluoro(2-bromoethyl vinyl ether) |
-
1986
- 1986-09-19 IT IT21759/86A patent/IT1197821B/en active
-
1987
- 1987-09-14 JP JP62228671A patent/JP2517313B2/en not_active Expired - Lifetime
- 1987-09-14 US US07/095,674 patent/US4772756A/en not_active Expired - Lifetime
- 1987-09-18 EP EP87201882A patent/EP0260773B1/en not_active Expired
- 1987-09-18 CA CA000547270A patent/CA1304415C/en not_active Expired - Lifetime
- 1987-09-18 ES ES198787201882T patent/ES2037704T3/en not_active Expired - Lifetime
- 1987-09-18 DE DE8787201882T patent/DE3775867D1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| IT8621759A1 (en) | 1988-03-19 |
| EP0260773A3 (en) | 1989-05-10 |
| EP0260773A2 (en) | 1988-03-23 |
| DE3775867D1 (en) | 1992-02-20 |
| ES2037704T3 (en) | 1993-07-01 |
| JPS63132851A (en) | 1988-06-04 |
| IT8621759A0 (en) | 1986-09-19 |
| EP0260773B1 (en) | 1992-01-08 |
| JP2517313B2 (en) | 1996-07-24 |
| IT1197821B (en) | 1988-12-06 |
| US4772756A (en) | 1988-09-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |